TW467928B - Process for preparation of polyamide from dinitrile and diamine - Google Patents

Abstract

A two-step process for the production of polyamides from Α, ω-dinitriles and Α, ω-diamines involving the catalytic hydrolysis of the Α, ω-dinitrile by addition of water with simultaneous purging of the reactor (i.e., venting of ammonia and water vapor) in the first step followed by polymerization by addition of the Α, ω-diamine to the hydrolysate in the second step. Such a process is particularly useful in the production of poly(hexamethylene adipamide), i.e., nylon 6,6 from adiponitrile and hexamethylene diamine using lower catalyst levels during hydrolysis and resulting in reduced levels of bis(hexamethylene)triamine, BHMT, in the polymer.

Description

A7 467928 ________B7 V. Description of the invention (1) Inventive park The present invention relates to a two-step method for producing polyfluoreneamine from Λ, ω_dinitrile and diamine. More specifically, the present invention relates to a method for preparing polyamines, in which 'addition of water and simultaneous removal of water vapor (ie, pumping) to hydrolyze dinitrile, and then proceed by adding diamine to the hydrolysate Polymerization. BACKGROUND OF THE INVENTION Traditionally, poly (vinylamine) is produced by the condensation polymerization of a diacid (eg, adipic acid) and a diamine (eg, hexamethylenediamine) or by the polymerization of an enantamine (eg, ε-caprolactam) Prepared by polymerization. Other methods are known which involve the preparation of polyamidamine by the reaction of Λ-dinitrile and ω-diaminediamine in the presence of water. For example, U.S. Patent No. 2,245,129 to Greenewait et al. Discloses a two-stage process in which, in the first stage, a reaction mixture containing dinitrile, diamine, and water is heated in a closed reaction tank until a low molecular weight polymer is formed. Ammonium amine is 'after' in a second stage by heating under atmospheric pressure or low pressure to remove the released ammonia and excess water to form a larger molecular weight polyamine.

Shyu et al. U.S. Patent No. 4,739,035 discloses a two-step process for the production of polyfluorene from α, ω-dinitrile and diamine in the presence of water. In the presence of a catalyst, the reaction is carried out at an autogenous pressure and at a temperature sufficient to substantially hydrolyze the diwax, and thereafter, the diamine is added to the resulting hydrolysate. The resulting reaction mixture is heated at a temperature sufficient to initiate the polymerization reaction. During the hydrolysis step, it can be as high as about 10 weight. / 0 of diamine is present. After the dinitrile is substantially hydrolyzed, a major amount of diamine is added to reduce the formation of the diamine (if the diamine is hexamethylene diamine, the triamine may be bis (hexyl) triamine (BYMT)). The triamine content of the formed polyamines is from 200 to -4- This paper is suitable for financial standards (ci ^ A4 size ⑽χ 297). (Please read the precautions on the back before filling this page), '装 ------- 1— Order --------- line' · ~ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ^ S792q V. Description of the Invention (2) l3〇0 In the ppm range, the method of continuously adding diamine during the reaction period is used, and the triamine content is within 1420 to 1610 ppm range. The presence of triamine causes branching and cross-linking of polyamidamine, which can cause gelation and significant loss of polymer quality.

U.S. Patent No. 5,627,257 by Liehr et al. Discloses a two-step process which is said to further reduce the formation of triamines. In the first step, diamine was hydrolyzed under autogenous pressure until at least 85% of the hydrolysed product was dikimic acid before the diamine was added. This hydrolysis is performed in the presence of a catalyst system (at least one phosphorus oxo acid and / or at least one water-soluble calcium, zinc, manganese or pickle salt) in a weakly acidic medium. The pH of the hydrolysis reaction medium is adjusted by adding a sufficient amount of at least one saturated aliphatic or aromatic dicarboxylic acid. In the case of gradual pressure release, the acid solution from the first step is reacted with at least an equal molar amount of diamine in the second step. The ammonia and water are removed by increasing the pressure and temperature, and then polycondensed This mixture was obtained to obtain a spinnable polyamide. Achieve the effect of triamine content between 500 and 600 ppm. The disadvantage of this method is the use of a large amount of auxiliary catalyst. For example, the amount of dicarboxylic acid used is about 13% by weight based on the adiponitrile content. DETAILED DESCRIPTION OF THE INVENTION The present invention overcomes the shortcomings of known methods and proposes polyamidamine with a small amount of triamine impurities without using a large amount of auxiliary catalyst. More specifically, the present invention proposes a two-step method using a dicarboxylic acid as a catalyst, that is, adding π, ω-diamine and polymerizing after hydrolysis of α, ω-dinitrile, and it has been found that, compared to during hydrolysis, The newly proposed two-step method using a water scrubbing step and simultaneously removing water and ammonia is not used, and the polyamine product of the present invention has less triamine content. -5- No paper size ruler used National Standard A4 (210 X 297 mm) III Packing ---- 11 ^-Order ---------- Line ( First read the note on the back ^ before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 7 9 2. g A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Therefore 'The present invention proposes an improved method for producing polyfluoreneamine from α, ω_dinitrile and π, diamine, the steps include: (a) in the absence of Λ, ω-diamine, ω-dinitrile is contacted with water and a sufficient amount of catalyst in a reactor at a temperature and pressure sufficient to initiate the hydrolysis reaction of dinitrile for a period of time sufficient to make the hydrolysis conversion of ω_dinitrile at least 95%, where, Water is added during the hydrolysis reaction and the reactor gas is simultaneously removed to remove ammonia and water vapor; (b) diamine is added to the hydrolysate obtained in step (a); (c) hydrolysate and diamine The mixture is heated in the presence of water for a period of time sufficient to polymerize; and (d) thereafter recovering polyamines characterized by low triamine content. In one embodiment, this < 〇ί, ω-dinitrile is adiponitrile, α, ω-diamine is hexamethylene diamine, and the catalyst of the hydrolysis reaction is a mixture of linolenic acid and hypoquinic acid, wherein 'recovery Polyamine is poly (hexylhexamethylene diamine), which is characterized by a BMT content of less than 1,000 ppm. Mode for Carrying Out the Invention The method of the present invention includes a two-step dish method for producing polyphosphamide from at least one dinitrile and at least one α, ω-diamine. In the first step, in the presence of a catalyst in the reactor but without -diamine, the precipitated dinitrile is contacted with water at a temperature and pressure sufficient to initiate the hydrolysis reaction of α, ω-dinitrile. During the hydrolysis step, water was added to the reactor, and the amine formed during the hydrolysis and a portion of the water were removed by suction from the reactor. In the second step of the method of the present invention, the hydrolysate from the first step is contacted with the diamine at a temperature sufficient to initiate the polymerization reaction and form the polyamine.

(Please read the precautions on the back before filling out this page) -Pack 7-Ordering line ry '

. Generally, the pressure during the polymerization is gradually reduced and water and ammonia are removed (e.g., 'by pumping') to increase the molecular weight of the polyamide. The formula of the dinitrile usable in the method of the present invention is:

NC-R-CN

Among them, R is a divalent aliphatic (straight or branched), alicyclic or aromatic organic group having up to 20 carbon atoms. A preferred ruler is a divalent straight-chain aliphatic group having 2 to 8 carbon atoms. Representative π ^ -dinitrile includes adiponitrile, octonitrile, nitrile, sebaconitrile, 1,12-dodecyldinitrile, p-benzonitrile, methylglutaronitrile, and the like. The preferred dinitrile is adiponitrile D, which can be used in the method of the present invention. The ω-diamine formula is: r, hn-r-nh-r "where 'R is as previously defined, r, and R "'Is selected from hydrogen or a monovalent aliphatic, cycloaliphatic or aromatic group, respectively. R, and R, preferably fluorene, especially when a high molecular weight product is desired and obtained, a can be used in the method of the present invention The αω_ diamines include hexamethylenediamine, butyldiamine, 1,12-dodecyldiamine, and p-xylylenediamine. The preferred α, ω-diamine is hexamethylenediamine. Used in the hydrolysis step The catalyst can include any substance that can promote the hydrolysis reaction of nitriles. Without a catalyst, the hydrolysis reaction is slow and results in an increase in decomposition products. Representative types of catalysts can include oxygen-containing phosphorus compounds, oxygen-containing boron compounds, and oxygen-containing compounds. Sulfur compounds, compounds containing metals (such as copper or copper), aliphatic and aromatic carboxylic acids, Lewis acid, etc. Specific examples of catalysts include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, sodium hypophosphite Hydrate, manganese (II) hypophosphite monohydrate, sodium calcium hypophosphite, sulfuric acid, aminosulfonic acid, sodium hydrogen sulfate, Ammonium bisulfate, phosphotungstic acid hydrate, phosphomolybdic acid hydrate, zinc acetate This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) f Please read the notes on the back before filling in this page ) ^ i!-Order ---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Online Economy 4 6 7 9 2 8 A7 _ B7 V. Description of the invention (5) Dihydrate, zinc sulfate heptahydrate, copper acetate (Π) Monohydrate, Acetic acid, Acetic acid, Glycolic acid, Lanthanum triflate, Manganese acetate (11) Tetrahydrate, Geeryl dimethyl desertification bell, 1 2_Fansalic acid hydrate And their mixtures. In the present invention, an effective amount of catalyst must be used to promote the hydrolysis reaction. The effective amount of catalyst depends on the type of catalyst. Basically, it ranges from 0 to 500 millimolar catalyst / mole. In the scope of the nitrile industry, in the present invention, 'water is used as a reactant for the hydrolysis reaction of nitrile in the first step, and as a processing elixir for polymerization in the second step. The amount of water used in the hydrolysis step must be at least equal Stoichiometry of the dinitrile to be hydrolyzed. Basically an excess of water is used. The hydrolysis reaction starts At the time, about L000 mol 0 / 〇 water can be added together with dinitrile. In the hydrolysis step, the dinitrile, water and catalyst are in a temperature range of 200 to 300 " c (preferably between 220 C and 280 ° c) ) Heat while scrubbing by pumping water into the reactor and removing a portion of the added water (in the form of water vapor) by pumping. The ammonia formed during the hydrolysis is also removed during pumping. For The reactor design is not strictly required. This reactor can be a stirred autoclave, a non-stirred autoclave, a column reactor, a tubular reactor, a loop reactor, etc. This method is usually carried out under airless conditions. Air can be removed by any known method. Examples include scrubbing the reactor with inert gas (including nitrogen or argon), evacuating and filling the reactor with inert gas, and pressurizing the reactor with inert gas. Pump down to i atmosphere or something. If necessary, multiple people can repeat these procedures. The temperature range of this method is determined by the hydrolysis reaction rate. The temperature is below 200. (:, The hydrolysis reaction rate is usually too low to use economically. When the temperature exceeds 300X, a large amount of by-products will be formed. During the reaction, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back of Jing before filling out this page.) Packing ---!! ^ --- J! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ β 7 928

The reaction temperature can be kept stable or changed. The rate at which water is added to the reaction varies depending on the reaction scale, reactor size, reactor design, reaction temperature, and the like. Generally, the 'water addition rate is in the range of 0.001 to 100 mol water plant', hour / mol dinitrile. In a preferred case, the water is added at a rate ranging from 0.1 to 1 mole water / hour / molar dinitrile. Water scrubbing can be started at any stage of the hydrolysis process. During the hydrolysis period, the scrubbing rate can be maintained stable or can be changed 'or scrubbing can be started or stopped during the hydrolysis period. The reaction pressure during the hydrolysis period is maintained at about 2 5 _;!, 000 psig a reaction pressure can be adjusted by suction setting. The length of hydrolysis time is related to the reaction temperature, method design, type and amount of reaction catalyst, and so on. The reaction time must be long enough to effectively hydrolyze at least 95 mole% nitrile groups. Preferably, this time should be long enough to effectively hydrolyze at least 98 mole% nitrile groups. In the second step of the present invention, a diamine is added to the hydrolysate formed in the first step and polymerized to form a polyamine. The amount of this &, ω-diamine added was within the range of j mol% based on the initial number of mols of ω-dinitrile. The exact amount is determined by the desired molecular weight, reactor design, dinitrile loss during the hydrolysis procedure, diamine loss during the polymerization procedure, and the like. In the preferred case, the polyamide formed has residual amine end groups or a slight excess of acid end groups to obtain a high molecular weight polyamide. It has been known that some of the dinitriles will be consumed during the hydrolysis step due to the formation of cyclohexanone. The cyclohexanone formed is volatile and can be removed when the reactor is scrubbed with water. Therefore, it has been found that when the amount of diamine is less than the initial π-dinitrile mole number, the polymer quality is improved because the amount of amine and acid end groups 酸 and the amount of BΗMT in the polymer is reduced. Other substances (such as water, stabilizers, polymerization catalysts, and processing aids) can be -9- This paper size applies to Chinese National Standards (CNS) ^^ (2) ϋ 7 mm) (Please read the note on the back first (Please fill in this matter again) ———————— Order · ---- Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Online Economics Α7 Β7 467928 V. Description of Invention (7) Added with diamine. Adding water to the diamine helps move all the diamine to the reactor. All diamines can be added at the beginning of the polymerization step, or the diamines can be added one by one during the polymerization reaction. This polymerization process involves heating the hydrolysate 'diamine and water from the first step at a temperature of about 200eC to 350eC. The temperature range of this method is determined by the polymerization reaction rate and the melting point of the polymer product. There are no strict requirements for the design of the reactor. This reactor can be the same as or different from the one designed for the hydrolysis procedure. This method is usually performed in the absence of air. Air can be removed by any known means, including those described in the hydrolysis step. The pressure of the polymerization procedure may be in the range of 0 to 1,000 psig or may be carried out under empty conditions. This pressure can remain stable or change during the polymerization process. Usually, the pressure decreases during the polymerization reaction. The reaction time required to form the polymer is related to the specific reactants, desired products, reaction temperature, reaction pressure, and the like. Generally, the polymerization process takes 0.1 to 10 hours. Specific temperature / pressure conditions will generally depend on the specific reactants used and the desired product. It has been found that when using the inventive method to prepare poly (hexyl adipamide) from hexamethylene nitrile hydrolysate and hexamethylene diamine, the polymerization procedure may include heating the reactants to 250 to 310 ec with a dust force between 200 and 300 psig (Set by air extraction), then reduce the pressure to atmospheric pressure and adjust to a temperature range of about 250 to 310 ° C. Test method: In the following examples, the composition of the reaction mixture obtained by the hydrolysis of adiponitrile was determined by high pressure liquid chromatography (HPLC) analysis equipped with a UV detector. This method did not detect adiponitrile in the reaction mixture. The reported weight% of reaction product is based on the total hydrolysate weight. -10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Γ Read the precautions on the back before filling in this page) Packing ------------ Order ---- ------ Line ΓΥ. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 46792g A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (8) John Wiley & Sons, Inc. in 1973 The "EncyclOpedia 〇f Industrial Chemical Analysis" published in the year of 2017 analyzes the poly (hexylhexamethylenediamine) amine and Acid terminal group. The relative viscosity (RV) of the polyamide sample refers to a 2.5 ° viscosity of a solution of 8.4% by weight polymer in 90.0% formic acid and 10% by weight water. The ratio between the viscosities of C. The bis (hexyl) triamine (BHMT) content of a polyamidohydrolyzate prepared by hydrolyzing polyamidoamine in hydrochloric acid was determined by gas chromatography (GC) analysis. Example 1 This example illustrates the cooperation of a group of For the hydrolysis catalyst, the hydrolysis reaction of adiponitrile at 27 (rc. Adiponitrile (150.00 g, 1.39 mol), water (125,00 g, 6,94 mol), phosphoric acid (0.075 g) and times A mixture of calcium phosphate (0.027 g) was added to a 1 liter stainless steel autoclave at room temperature. This autoclave was released after nitrogen was pressurized to 60 psig. Repeat this operation 6 times. After the last pressure release, stir The reaction mixture was heated to 270 ° C. After reaching 27 CTC, water was pumped into the autoclave at a rate of 1 ml / min. The reaction pressure during the experiment was maintained between 608 and 60 psi. 514 psig. After 27 hours with water stripping, stop purging with water and allow the closed autoclave to cool to room temperature. Samples of the autoclave contents were analyzed by HPLC. The HPLC analysis results are listed below Schedule 1. The presence of gambling compounds in the hydrolysate was not detected.

Comparative Example A This example illustrates the use of a combination of phosphoric acid and calcium hypophosphite as a hydrolysis catalyst. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). {谙 Notice on the back of Jing Jing # .Fill in this page) Install --------- Order --------- A7 46792b -------- B7______ 5. Description of the invention (9) Dinitrile at 27 ° C. Hydrolysis reaction in a closed reactor under autogenous pressure. A mixture of adiponitrile (150.00 g, 1.39 mol), water (125.00 g, 6.94 mol), phosphoric acid (0.075 g), and calcium hypophosphite (〇27 g) was added to 1 liter of stainless steel at room temperature In an autoclave. This autoclave was vented after pressurizing to 60 psig with nitrogen. Repeat this operation 6 times. While stirring, heat the autoclave to 270. (:. After reaching 270 ° C, the maximum autogenous pressure was observed to be 635 psig. During this operation, the pressure slowly decreased to the final 48i psig. After 270x: After 2 hours, the autoclave was cooled to room temperature. Autoclave The contents of the reactor were analyzed by HPLC. The results of HPLC analysis are shown in the following Appendix 1. The results of Example 1 and Comparative Example a show that the hydrolysis reaction was performed in a closed reactor with water scrubbing and autogenous pressure for comparison. The conversion of the nitrile fraction was improved. No nitrile-containing compound was measured in the hydrolysate of Example 1, while the hydrolysate of Comparative Example A contained 16.4% by weight of 5-nitrylpentamidine and 16.3% by weight of 5-nitrilepentyl. Example 2 This example illustrates the adiponitrile at 230X in a suction reactor maintained at a pressure of between 347 and 318 psig with water scrubbing, using a combination of phosphoric acid and hypophosphonic acid as the hydrolysis catalyst. : Hydrolysis reaction. A mixture of adiponitrile (150.00 g, 1.39 mol), water (125'00 g, 6.94 mol), phosphoric acid (0.075 g) and calcium hypophosphite (0.027 g) is added to 1 at room temperature. Liter stainless steel autoclave. This autoclave is pressurized with nitrogen Depressurize after 60 psig. Repeat this operation 6 times. Heat the press to 230 while stirring. (:. After reaching 230 ° C, water is pumped into the autoclave at a rate of 1 ml / min for scrubbing. The reaction pressure during the experiment was maintained between 347 and 318 psig by pumping down the air. After 230 ° 06 hours, stop using water to purify the gas, so that the pressure is -12- This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the note on the back before filling out this page) Install ----! | Order --------. Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 467928. A7 B7 V. Description of the invention (10) The heater is cooled to room temperature. Samples of the contents of the autoclave are analyzed by HPLC. HPLC analysis results are listed in the attached table below. 1. The hydrolyzate does not contain detectable 5-nitronitramide, and contains 1.6% by weight of 5-nitrivalic acid. Example 3 This example demonstrates that the pressure of water scrubbing is maintained between 330 and 277 psig When the combination of squamous acid and hypophosphorous acid was used as the hydrolysis catalyst in the extraction reactor between Hydrolysis reaction at ° C. A mixture of adiponitrile (150.00 g, 1.39 mol), water (125_00 g, 6.94 mol), phosphoric acid (0,075 g), and subscale: acid fishing (0.027 g) in Add to room temperature to a 1 liter non-steel autoclave. Repeat the procedure of Example 2. However, during the experiment, the reactor pressure was maintained between 330 and 277 psig. Pressure: The contents of the autoclave were analyzed by HPLC. analysis. The results of the HPLC analysis are shown in Table 1 below. The hydrolyzate did not contain detectable 5-nitrylpentanamine and contained 1.4 wt. Of nitrile valeric acid. Example 4 This example illustrates the adiponitrile at 230 ° C in a gas extraction reactor maintained at a pressure between 259 and 206 psig with a combination of phosphonic acid and hypophosphonic acid # 5 as the hydrolysis catalyst. C hydrolysis reaction. A mixture of adiponitrile (150,00 g, 1.39 mol), water (125.00 g, 6.94 mol), phosphoric acid (0.075 g), and calcium hypophosphite (〇_027 g) was added to 1 liter of stainless steel at room temperature. In the heater. The procedure of Example 2 was repeated, but the reactor pressure was maintained between 259 and 206 psig during the experiment. Samples of the autoclave contents were analyzed by HPLC. The results of the HPLC analysis are shown in Table 1 below. The hydrolyzate does not contain detectable 5-nitrylpentanamine, and it contains 0.5% by weight 5 -nitrile. This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read first (Notes on the back, please fill out this page)

I 4 6 7 92 B A7 __—_ B7 V. Description of the invention (11 Example of valproic acid 5 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This example shows that the pressure of cleaning with water is maintained between 329 and 29 lpsig In the extraction reactor of ‘with calcium hypophosphite as the hydrolysis catalyst, the hydrolysis reaction of adiponitrile at 230 ° C. adiponitrile (150.00 g, 1.39 mol), water (125.00 g, 6.94 mol), and A mixture of calcium hypophosphite (0.183 g) was added to a 1 liter stainless steel autoclave at room temperature. The procedure of Example 2 was repeated, but the reactor pressure was maintained between 329 and 291 psig during the experiment. Autoclave The content samples were analyzed by hplc. The results of HPLC analysis are listed in the attached Table 1 below. This hydrolysate contains 1.0% by weight of 5-nitrylpentanamide and 1.6% by weight of 5-nitrivalic acid. Nitrile conversion Lower than the one obtained in Example 3 using a combination of calcium hypophosphite and phosphoric acid catalyst. Example 6 This example illustrates a suction reactor maintained at a pressure of between 324 and 305 psig with water scrubbing gas. When half the amount of calcium hypophosphite is used as a hydrolysis catalyst, the hydrolysis reaction of adiponitrile at 230 ° C A. A mixture of adiponitrile (150.00 g, 1.39 mol), water (125.00 g, 6.94 mol) and crane hypophosphite (0.091 g) was added to a 1-liter non-steel autoclave at room temperature. Repeat The procedure of Example 5 'But during the experiment, the reactor pressure was maintained between 324 and 305 psig. Samples of the autoclave contents were analyzed by jjPLC. The results of the HPLC analysis are listed in Appendix 1 below. This hydrolysate contains 6 wt.% 5-nitrivalyl amine and 1-4 wt% 5-nitrival valeric acid. The conversion rate of nitrile group is lower than that obtained in Example 3 using a combination of calcium hypophosphonate and phosphoric acid catalyst. Example 7 • 14-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page} tn Read 5 «. 4 6 7 928 A7 Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (12) This example shows that when adipic acid is used as the hydrolysis catalyst in an aspirating reactor maintained at a pressure between 3 59 and 299 psig with water scrubbing gas, Hydrolysis reaction of nitrile at ° C. Adiponitrile (150.00 g, 1.39 mol), water (125.00 g 6.94 mol) and adipic acid (22.50 g, 0.15 mol) were added to a j-liter stainless steel autoclave at room temperature. The procedure of Example 2 was repeated, but the reactor pressure was maintained between Between 359 and 299 psig. Samples of autoclave contents were analyzed by HPLC. The results of HPLC analysis are listed below in Table 1. This hydrolysate does not contain the detected 5-nitrilepentanamide and contains __ 1 5% Nitrilevaleric acid by weight. Example 8 This example illustrates the hydrolysis reaction of adiponitrile at 23 ° C in a gas extraction reactor maintained at a pressure of between 332 and 266 psig with zinc sulfate as the hydrolysis catalyst. A mixture of hexamethylene chloride (150.00 g, 1.39 mol), water (125.00 g, 6.94 mol), and zinc sulfate heptahydrate (0.309 g) was added to a [liter] stainless steel autoclave at room temperature. The procedure of Example 2 was repeated, but the reactor pressure was maintained between 332 and 266 psig during the experiment. Samples of the autoclave contents were analyzed by HPLC. The results of the HPLC analysis are listed in Appendix J below. This hydrolysate contained 0.4% by weight of 5-nitrivalylamine and 1.1% by weight of 5-nitrivalyl acid. -15- ‘Paper size applies Chinese National Standard (CNS) A4 specification (21〇297 mm) (Please read the note on the back #, fill out this page) —Order —— 4 6 7 92 8 A7 B7 V. Description of the invention (13) Table 1 Product analysis <1> Example Example Adipic acid diamine adipic acid 5_Cyclopentamic acid adipic acid 5_ Cyanovaleric acid (wt%) (wt%) (wt%) (wt%) (wt%) 26.8 ND (a) 9.7 25-1 16.4 6.4 3 3.0 ND 33.5 0 ND 39.2 9 ND 39, 2 1.0 26 1 0.6 35 1 ND 36 5 0.4 34.1

1 A 2 3 4 5 6 7 S 11.9 13.7 13.4 9.2 10.6 17.5 12.4 11.0 12.9 29 31 35 33 32 34 7 8 ND 16.3 6 4 0 (Please read the notes on the back before filling this page) Consumer Cooperatives printed (a) &quot; ND &quot; on behalf of failure to measure (b) The number listed is the average of two determinations. Example 9 This example illustrates the two-step method of the present invention. In the case of water scrubbing, using phosphoric acid and calcium hypophosphite as catalysts, hydrolyze adiponitrile, and then add hexamethylene diamine and polycondensate to form poly (di-hexyl adipamide diamine). A mixture of adiponitrile (39.00 g, 0.36 mol), water (32.40 g, 1.80 mol), phosphoric acid (0.22 g), and calcium hypophosphite (0.007 g) was added to 300 ml of stainless steel. In the heater. This autoclave was depressurized after it was pressurized to 300 psig with nitrogen. Repeat this operation 3 times. After that, the autoclave was pressurized with nitrogen to 300 psig. -16- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) 0X 297 mm> 467928 A7 B7 V. Description of the invention (14) 'Evacuation reduces the pressure to 20 psig nitrogen pressure. Heat to 25 ° C while stirring. After reaching 250 C, the strip water is pumped into the waste heat exchanger at a rate of 6 cubic centimeters per hour. The reactor pressure was maintained at 25 psig during the period. After 6 hours at 250 ° C, the water purifier was stopped and the autoclave was cooled to room temperature. The autoclave was turned on and hexamethylenediamine (40.20 g, 0.35 mol) was added. ) And water (25,000 grams). Release pressure from the autoclave and pressurize to 300 psig with nitrogen. Repeat this operation 3 times. After pressurizing the autoclave to 300 psig with nitrogen, Evacuation reduces the pressure to 20 psig nitrogen pressure. The autoclave is heated to 275 ° C while stirring, and the evacuation is set to 250 psig. After reaching 275 ° C, the pressure is reduced to atmospheric pressure in 1 hour. At atmospheric pressure, The polymerization was terminated at 275 ° C for 45 minutes, and then the autoclave was cooled to room temperature. The relative viscosity (RV) of the obtained product was analyzed. Terminal groups and bis (hexyl) triamine (BHMT) content, the results of which are listed in Table 2 below. Example 1 0 Adiponitrile (39.00 g, 0.36 mol), water (32_40 g, 1.80 mol) A mixture of phosphoric acid (0.02 g) and calcium hypophosphite (0.007 g) was added to a 300 ml stainless steel autoclave. The hydrolysis procedure of Example 9 was repeated, but the rate of pumping water for scrubbing into the autoclave was 6 Cubic centimeters / hour changed to 9 cubic centimeters / hour. After hydrolysis, turn on the autoclave and add hexamethylenediamine (40.20 g, 0.35 mol) and water (5.0 g). After the autoclave released the pressure, use the example 9 The procedure described above was used to perform a polycondensation reaction. The relative viscosity (RV), terminal groups, and bis (hexyl) triamine (BHMT) content of the obtained product were analyzed, and the results are listed in Appendix 2 below. Example 1 1 Adiponitrile ( 39.00 grams, 0-36 moles), water (32.40 grams, 1.80 moles), phosphorus-17- This paper is again suitable for China National Standard (CNS) A4 (210 X 297 mm) (Please read the back (Notes should be filled out on this page) .....- Printed by A7 467928, Employee Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs ______ B7___ 5. Description of the invention (15) A mixture of acid (0.02 g) and calcium hypophosphite (0.007 g) was added to a 300 ml stainless steel autoclave. Repeat the hydrolysis procedure of Example 9. After hydrolysis, turn on the autoclave. Hexanediamine (40.3 g '0.35 mole) and water (25.0 g) were added. The autoclave was depressurized. The autoclave was pressurized with nitrogen to 300 pSig and then depressurized. Repeat this operation 3 times. The autoclave was pressurized with nitrogen to 300 psig and evacuated to 20 pSig nitrogen pressure. The autoclave was heated to 275 eC while stirring and the evacuation was set to 250 psig. After reaching 275 ° C, the pressure was reduced to 20 psig over an hour. After that, the autoclave was pressurized to psig with nitrogen and then cooled to room temperature. The relative viscosity (RV), terminal groups and bis (hexyl) triamine (BHMT) content of the obtained product were analyzed. The results are shown in Table II below.

Comparative Example B This example was performed under conditions similar to Example 9, but using stoichiometric hexamethylenediamine based on the amount of starting adiponitrile. A mixture of adiponitrile (39.00 g, 0.36 mol), water (32.40 g, 1.80 mol), phosphoric acid (0.02 g), and hypophosphite conversion (0.007 g) was added to a 300 ml stainless steel autoclave. . The hydrolysis procedure of Example 9 was repeated. After the hydrolysis, the autoclave was turned on and hexamethylene diamine (41.60 g &apos; 0.36 mole) and water (5.00 g) were added. The pressure of this autoclave was released and the polymerization procedure described in Example 9 was repeated. The relative viscosity (RV), terminal groups and bis (hexyl) triamine (BHMT) content of the obtained products were analyzed, and the results are shown in Appendix 2 below. Compared to Example 9, which reduced the amount of diamine by taking into account the loss of adiponitrile during the hydrolysis reaction period, the rV of the polyfluorene amine formed using the stoichiometric hexamethylene diamine based on the initial adiponitrile amount Much lower and contains a large number of amine end groups. Example 1 2 -18-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ^ &amp; 1 ··· ιιϋ_Γ First: Yi.fei: r '-J Pack ------ , —Yes --------- (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 467928 __B7_ V. Description of the invention (16) Adiponitrile ( A mixture of 6375.05 grams, 58.8 moles), water (5305.66 grams, 294.8 moles), phosphoric acid (3.19 grams), and calcium hypophosphite (L15 grams) was added to a 35-gallon stainless steel autoclave. This autoclave was purged with nitrogen When stirring, it was heated to 25 ° C. After reaching 25 ° C, the water for scrubbing was pumped into the autoclave at a rate of 30 cm / min. By pumping, the reaction pressure during the experiment was maintained at 250 psig. After 6 hours at 250 ° C, stop purging with water and allow the autoclave to cool to room temperature. Turn on the autoclave and add 78.34% by weight aqueous hexamethylene diamine solution (8744.95 g, 58_96 mole hexamethylene diamine). The autoclave is depressurized and vented with nitrogen. The autoclave is heated to 275 ° C during the stirring time, and the evacuation is set to 250 psig. After reaching 275 ° C The pressure was reduced to atmospheric pressure in 1 hour. The polymerization reaction was terminated at atmospheric pressure and 275T for 30 minutes. The polymer was then extruded from an autoclave. The relative viscosity (RV), terminal group content, and di (hexyl) of the obtained polymer were analyzed. ) Triamine (BHMT) content, the results are listed in the attached Table 2. Table 2 Examples of polymer analysis results RV amine terminal group acetic acid terminal group BΜΕΓΓ (Please read the precautions on the back before filling in this purchase)! 丨丨! Order ---- ^. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-10,000 grams of polymer) (Mole / Million grams of polymer) 9 69 34 64 365 10 40 25 99 752 11 34 82 77 880 12 37 50 64 623 B 13 317 13 1720 (a) Molar number per million grams of polymer -19- 4 6 7 928 A7 B7_V. Description of the invention (17) has been described and based on certain characteristics Given the examples of the present invention, it should be understood that the scope of the following patent applications is not intended to be restrictive, and is only used to correspond to the elements described in the patent application park and equivalent items. (Please read the precautions on the back before filling this page ) 丨 installed ------,-. Tr -----

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Claims (1)

467928 Patent scope 2. A method for producing polyamidoamine from α, ω-dinitrile and ", ^-diamine ', the steps of which include: (a) in the absence of α, ω ~ diamine, Contact Shen, ω-dinitrile with water and a sufficient amount of catalyst in a reactor at a temperature and pressure sufficient to initiate the hydrolysis reaction of dinitrile-the segment is sufficient to hydrolyze Shen, ω-dinitrile; # 化 率 是 9 5 % Time, wherein during the hydrolysis reaction, water is added and the reactor gas is simultaneously pumped to remove ammonia and water vapor; (b) diamine is added to the hydrolysate obtained in step (a); ( c) the mixture of the hydrolysate and the diamine is heated in the presence of water for a period of time sufficient to polymerize; and (d) the polyamine, which is characterized by a low triamine content, is recovered. The method according to item 1 of the scope of the patent application, wherein the Λω —dinitrile is adiponitrile, the -diamine is hexamethylene diamine, the catalyst used for the hydrolysis reaction is a mixture of phosphoric acid and calcium hyposcale acid, and wherein the recovered polyamidoamine is characterized by a BΗMT content Less than 1,000 ppm of poly (hexyl adipamide). (Please read the unintentional matter on the back before clearing it. (Fill in this page) ^ ------- Λ— Order V .------- Line r Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-21-Wood paper standards are applicable to China National Standard (CNS) A4 Specifications ⑽χ 297 public love)